Metallic substrate having an adherent photo-product coating on its surface and a method of coating said metallic substrate

ABSTRACT

This invention relates to a metallic substrate having on its surface an adherent photo-product coating, and a method for coating that substrate, which coating is formed by exposing to light in the presence of an oxygen source, a reactant mixture comprising: 2,2&#39;4,4&#39;-tetrahydroxybenzophenone, with (1) ammonium hydroxide and optionally a trace amount of at least one reactive metal, or (2) ammonium hydroxide and at least one metal salt, or (3) at least one metal salt and at least one amine, or (4) ammonium hydroxide, at least one metal salt and at least one amine; in a suitable solvent.

This application is a continuation-in-part of application, Ser. No. 003,350, filed 01/14/87, now U.S. Pat. No. 4,794,131 entitled "A Photo-Product Energy Barrier Composition".

The present invention relates to a substrate having an adherent photo-product coating, and a method for coating a substrate with that photo-product composition. More particularly, it relates to a photo-product coating adhered to the surface of a metallic substrate, and a method for producing such a structure by coating a metallic substrate with a substituted benzophenone reactant mixture which is exposed to light in the presence of an oxygen source.

It has long been desired to provide an effective coating for metallic substrates. Such coatings have the potential to alter the chemical, physical and/or electrical properties of the metallic substrate. Conventional films typically lack the desired adherency characteristics to accomplish these objectives.

Benzophenones and substituted benzophenones are well known as ultraviolet light absorbers. See for example, BASF Wyandotte Corporation's Technical Data entitled "UVIMUL UV Absorbers, For Cosmetics, Plastics, Coatings, Textiles", which discloses numerous substituted benzophenones, and 2,2',4,4'-tetrahydroxybenzophenone in particular, as useful absorbers of ultraviolet light for a variety of applications. Additionally, Smallwood et al., U.S. Pat. No. 3,296,191, discloses that thermally-produced nickel or cobalt derivatives of specified hydroxybenzophenones, which do not include 2,2',4,4'-tetrahydroxybenzophenone, are useful as light and heat stabilizers for polypropylenes. The disclosed benzophenones are 2,2'-dihydroxy-4-alkoxybenzophenones with C₆ -C₂₀ alkyl radicals being required for effective stabilization. Additionally, the coordination complex contains no more than about one mole of metal for every two moles of benzophenone.

U.S. Pat. No. 2,989,416 to Standish, however, states that these materials, in general, are not entirely satisfactory because of the difficulty in applying them to surfaces and the relative ease by which they are washed from such surfaces. Standish addresses such problems by reacting certain ortho-hydroxyl substituted benzophenones, with a trivalent metal, either chromium or aluminum, in molar ratios of benzophenone to metal ranging from 1:0.5 to 1:10 to form water-soluble Werner complexes that absorb longer wavelength ultraviolet radiation. The Standish product is a thermally produced compound, not a composition produced by a photo reaction.

More specifically, it is an object of this invention to provide a metallic substrate having on its surface an adherent photo-product coating.

Still more specifically. it is an object of this invention to provide a photo-product coating that strongly adheres to metallic substrates including steel, titanium, tungsten, copper, iron, platinum, nickel, gold, aluminum, silver, zinc and the like.

Additionally, it is an object of this invention to provide a method of cleaning metallic substrates by applying and then removing this photo-product coating.

These and additional objectives are shown from the description below.

SUMMARY OF THE INVENTION

In the substrate embodiment, this invention consists of a metallic substrate having on its surface an adherent photo-product coating, which coating is formed by exposing to light in the presence of an oxygen source, a reactant mixture ("Reactant Mixture I") comprising (a) 2,2',4,4'-tetrahydroxybenzophenone, (b) ammonium hydroxide, and (c) optionally a trace amount of at least one reactive metal, in a solvent.

In a further substrate embodiment, the reactant mixture ("Reactant Mixture II") comprises (a) 2,2',4,4'-tetrahydroxybenzophenone, (b) ammonium hydroxide, and (c) at least one metal salt, in a solvent.

In still another substrate embodiment, the reactant mixture ("Reactant Mixture III") comprises (a) 2,2',4,4'-tetrahydroxybenzophenone, (b) at least one metal salt, and (c) at least one amine, in a solvent.

In still a further substrate embodiment, the reactant mixture ("Reactant Mixture IV") comprises (a) 2,2',4,4'-tetrahydroxybenzophenone, (b) ammonium hydroxide, (c) at least one metal salt, and (d) at least one amine, in a solvent.

In the method embodiment, this invention consists of a method of forming an adherent photo-product coating on the surface of a metallic substrate comprising the steps of (1) preparing a reactant mixture comprising (a) 2,2',4,4'-tetrahydroxybenzophenone, (b) ammonium hydroxide, and (c) optionally a trace amount of at least one reactive metal, in a solvent; (2) contacting said substrate with said reactant mixture; and (3) exposing said reactant mixture in contact with said substrate to light in the presence of an oxygen source. ("Method of Reactant Mixture I").

In another method embodiment, the reactant mixture comprises (a) 2,2',4,4'-tetrahydroxybenzophenone, (b) ammonium hydroxide, and (c) at least one metal salt, in a solvent. ("Method of Reactant Mixture II").

In still another method embodiment, the reactant mixture comprises (a) 2,2',4,4'-tetrahydroxybenzophenone, (b) at least one metal salt, and (c) at least one amine, in a solvent. ("Method of Reactant Mixture III").

In still a further method embodiment, the reactant mixture comprises (a) 2,2',4,4'-tetrahydroxybenzophenone, (b) ammonium hydroxide, (c) at least one metal salt, and (d) at least one amine, in a solvent. ("Method of Reactant Mixture IV").

In the method of cleaning embodiment, this invention consists of a method of cleaning a metallic substrate comprising the steps of (A) forming an adherent photo-product coating on the surface of said substrate by (1) preparing any of the above I-IV reactant mixtures; (2) contacting said substrate with the reactant mixture; and (3) exposing the reactant mixture in contact with said substrate to light in the presence of an oxygen source; and then (B) removing said photo-product coating from the surface of said substrate.

It has been surprisingly found that 2,2',4,4'-tetrahydroxybenzophenone (THBP) in combination with (1) ammonium hydroxide, or (2) ammonium hydroxide and at least one metal salt, or (3) at least one metal salt and at least one amine, or (4) ammonium hydroxide, at least one metal salt and at least one amine; in a suitable solvent, produces an adherent photo-product coating on the surface of a metallic substrate upon exposure to light in the presence of oxygen.

The coating of metallic substrates has the potential to alter the chemical, physical and/or electrical properties of the metallic substrate.

It has been additionally found that the photo-product coatings of this invention tenaciously adhere to many substrates, including steel, titanium, tungsten, copper, iron, platinum, nickel, gold, aluminum, silver, zinc and the like, and are insoluble in water and many organic solvents and therefore resist removal from these substrates once applied.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the infrared absorption spectrum for the photo-product coating of claim 8.

FIG. 2 is the infrared absorption spectrum for the photo-product coating of claim 9.

FIG. 3 is the infrared absorption spectrum for the photo-product coating of claim 10.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the invention consists of a metallic substrate having on its surface an adherent photo-product coating, which coating is formed by exposing to light in the presence of an oxygen source, a reactant mixture ("Reactant Mixture I") comprising (a) 2,2',4,4'-tetrahydroxybenzophenone; (b) ammonium hydroxide; and (c) optionally a trace amount of at least one reactive metal; in a solvent.

Additionally, the method of forming an adherent photo-product coating on the surface of a metallic substrate comprising the steps of (1) preparing Reactant Mixture I in a solvent; (2) contacting said substrate with said reactant mixture; and (3) exposing said reactant mixture in contact with said substrate to light in the presence of an oxygen source; is within the scope of this invention.

In this and other more preferred embodiments of this invention, the benzophenone found best to meet the objectives of this invention and provide a photo-product coating is 2,2',4,4'-tetrahydroxybenzophenone. Other benzophenones that do not yield the present photo-product coating include 2,2'-dihydroxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 4,4'-dihydroxybenzophenone; and 2,4'-dihydroxybenzophenone. These particular benzophenones were tested by the Method of Reactant Mixture IV and found to give various precipitants without producing a photo-product coating of this invention.

Additionally, certain sources of ammonium ion (NH₄ +) and hydroxyl ion (--OH) other than ammonium hydroxide have not proven effective in producing the photo-product coating of this invention. For example, benzyltrimethyl ammonium hydroxide, tetramethyl ammonium hydroxide, ammonium bromide and ammonium acetate, all failed to produce the requisite photo-product coating when utilized as substitutes for ammonium hydroxide in the Method of Reactant Mixture IV.

The reactive metal can be employed in elemental form or as an organic or inorganic compound, providing that it is capable of reacting with the solvated, ammoniated THBP. It is postulated that the reactive metal in its cationic form promotes formation of a stable photo-product. In certain cases, elemental metal, such as nickel, can be employed in powder form or the like. Such forms are adapted to be readily solubilized as an hydroxide or oxide. For most purposes, however, metal organoates or metal inorganic salts are preferred.

In the Method of Reactant Mixture I, a reactive metal need not be added to the mixture of reactants. X-ray analysis, however, has shown that when combining THBP and ammonium hydroxide in the presence of a solvent, trace amounts of reactive metals, in particular, zinc, are typically present as contaminants.

It is believed that the trace amounts of reactive metal assist in forming and stabilizing the photo-product. In the other reactant mixtures (mixtures II, III and IV), at least one metal salt is intentionally added to the mixture of reactants. Useful reactive metals, especially metal salts are provided hereafter in connection with the discussion of Reactant Mixture II.

The concentration of THBP and ammonium hydroxide utilized in accordance with this aspect of the invention varies from a molar ratio of 1:1 to about 20:1, with a molar ratio of 18 moles of THBP to about 5 moles of ammonium hydroxide being preferred.

The reaction is typically carried out at room temperature (approximately 22° C.). The reaction temperature is not critical, and the addition of heat is not necessary, nor is it a limiting factor in the photo-product reaction. However, with some reactant mixtures a heat treatment may be necessary to promote the solubilization of the reactants.

The photo reaction is carried out in the presence of light, such as sunlight or artificially produced ultraviolet radiation in the range of about 200 to 400 nanometers, with about 340 to 360 nanometers being preferred. The more intense the light, particularly light in the 340 to 360 nanometer range, the more rapid the formation of the photo-product. Artificial light in this range, e.g., light produced by a mercury arc lamp, enhances the rate of photo-product formation and can, under certain circumstances, provide a coating visible to the naked eye in a few hours. Additionally, this photo-product coating adheres less tenaciously to various substrates as compared with those of Reactant Mixtures II and IV. The coating of Reactant Mixture I is also dissolved by dimethyl formamide.

A visible photo-product coating of Reactant Mixture I forms slowly on a metallic substrate. While the photo-product can be detected almost instantly upon mixing the reactants under the proper conditions, it usually takes between about 2 and 3 days of exposure of Reactant Mixture I to direct sunlight before a film becomes noticeable to the naked eye.

According to this invention, photo-product coatings can be made by effecting contact of the substrate and the reactant mixture in a solvent. It is necessary only that the reation medium be such that each of the reactants are soluble in it. Water alone can be utilized, but does not impart sufficient solubility to yield optimum results. Other suitable solvents are alcohols, with preferred solvents including lower alkanols, such as ethanol, isopropanol, n-propanol, isobutanol, n-butanol, and the like. Aqueous alcohol solvents and various mixtures of these solvents can also be utilized.

An oxygen source within the scope of this invention is molecular oxygen. Air contains sufficient oxygen to meet the objectives of this invention. Generally, sufficient dissolved oxygen will be present if the surface of the reactant mixture is exposed to a source of gaseous oxygen. It has been observed that bubbling pure molecular oxygen through the reactant mixture speeds up the reaction rate. Other oxygen sources providing molecular oxygen may also be employed. The photo-product coating will not, however, form in the absence of oxygen. For example, Reactant Mixture IV, under a nitrogen or argon atmosphere in the absence of oxygen, did not produce a photo-product coating of the present invention.

The substrates that can be utilized in accordance with the teachings of this invention include metals and metal alloys. In general, these substrates exhibit the following characteristics--(1) good thermal and electrical conductivity, (2) opacity to ordinary light, (3) metallic lustre arising from the quality of reflected light, (4) ductility, (5) malleability, or the ability to flow under impact loading, and (6) formation of positive ions in acids. These substrates include steel, titanium, tungsten, copper, iron, platinum, nickel, gold, aluminum, silver, zinc and the like. The invention is not, however, intended to be limited by the above-listed substrate materials.

Suitable metal alloys useful in this invention include those formed from combinations of the previously listed metals. Typical alloys include nickel alloy, brass and aluminum alloy.

In addition, composites or laminates of metals and organic resins or compounds or inorganic compounds can also be employed.

FIG. 1 shows the infrared absorption spectrum of one particular Reactant Mixture I photo-product coating formed by exposure to fluorescent light in the presence of air for 5 days. The reactant mixture contained 1% ammonium hydroxide, 4% THBP and 95% ethanol. Trace amounts of zinc were detected in this photo-product by x-ray analysis. The infrared absorption spectrum of FIG. 1 was determined by placing a silver chloride plate in the above mixture, and leaving the plate and reactant mixture exposed to fluorescent light in a laboratory for 5 days in a normal atmospheric environment. After 5 days, the plate was removed, washed with ethanol, then washed with acetone, dried and placed into an FTIR instrument (a Nicolet model 60SX Fourier Transform Infrared Spectrometer).

In another substrate embodiment, this invention consists of a metallic substrate having on its surface an adherent photo-product coating, which coating is formed by exposing to light in the presence of an oxygen source, a reactant mixture comprising (a) 2,2',4,4'-tetrahydroxybenzophenone; (b) ammonium hydroxide; and (c) at least one metal salt; in a solvent. Additionally, the Reactant Mixture II method of forming an adherent photo-product coating on the surface of a metallic substrate is also within the scope of this invention.

The metal salts that can be utilized in accordance with this aspect of the invention include the metal cations zinc, cadmium, copper, silver, nickel, zirconium, palladium, platinum, cobalt, rhodium, iron, ruthenium, manganese, tin, lead, polonium, mercury, and the like, and mixtures thereof, in combination with various inorganic and organic anions, such as sulfate, nitrate, bromide, chloride, acetate, formate, benzosulfonate, benzoate, and carbonate, and the like, and mixtures thereof. The preferred metal salts include nickel chloride (NiCl₂.6H₂ O), cobalt chloride, silver acetate, copper chloride, iron chloride, zinc acetate, lead chloride and copper acetate. These metal salts should not be confused with the metallic substrate, although the metallic substrate may provide metal ions that become an active part of the reactant mixture.

The typical concentrations of the three reactants used to form Reactant Mixture II are as follows: THBP from about 0.01% to 10%, ammonium hydroxide from about 0.01 to 10%, and metal salt from about 0.001 to 5%. All weight percents are based on the weight of the total composition.

A preferred product is formed from a ratio of at least about 18 moles of THBP, 5 moles of ammonium hydroxide, and 1 mole of a metal salt, such as nickel chloride. The maximum concentration of reactants in the process, especially THBP, is limited by solubility.

The reaction conditions described above for Reactant Mixture I apply to Reactant Mixture II, except that the photo-product reaction proceeds at a faster rate. A noticeable film is usually observed within 24 hours upon exposure to sunlight in the presence of oxygen. It is postulated that the addition of the metal salt permits the formation of an intermediate metal ligand-coordination complex which improves both the energy barrier properties of the Substrate of Reactant Mixture II and the rate of reaction.

The rate of reaction is, as previously explained, dependent on the type and intensity of light. However, the rate of reactivity is, in general, also dependent on the metal cation utilized, with the general order of reactivity (from fastest to slowest) as follows: manganese (Mn⁺²), ruthenium (Ru⁺²), iron (Fe⁺²), rhodium (Rh⁺²), cobalt (Co⁺²), platinum (Pt⁺²), palladium (Pd⁺²), copper (Cu⁺²), lead (Pb⁺²), nickel (Ni⁺²), cadmium (Cd⁺²), and zinc (Zn⁺²)

The photo-product coating of Reactant Mixture II is evidenced by the formation of a film with a metallic appearance which forms on the substrate that is in contact with the reactants. For example, if the reactants are mixed in a glass vial, the photo-product will form and tenaciously adhere to the glass vial upon exposure to light in the presence of oxygen.

This invention, in another substrate aspect, consists of a metallic substrate having on its surface an adherent photo-product coating, which coating is formed by exposing to light in the presence of an oxygen source, a reactant mixture comprising (a) 2,2',4,4'-tetrahydroxybenzophenone; (b) at least one metal salt; and (c) at least one amine; in a solvent. Additionally, the Reactant Mixture III method of forming an adherent photo-product coating on the surface of a metallic substrate is within the scope of this invention.

The amines that are used in accordance with this invention include triethanolamine, monomethanolamine, ethanolamine, diethanolamine, butylamine, n-amylamine, and the like. In the absence of ammonium hydroxide, it is believed that the amine's sole function, in particular the preferred amine, triethanolamine, is assisting in the deprotonation of THBP prior to the photo-reaction. Regardless of the presence or absence of ammonium hydroxide, however, the amines mentioned above, including others, also have the capacity to form an amine metal coordination complex, which is believed to complex with the deprotonated THBP during the process. Additionally, the amine-metal complex hinders the formation of insoluble metal hydroxides.

Reactant Mixture III can be conveniently utilized in commercial use. However, to inhibit the photo-reaction from occurring prior to application by the user, a stabilized formulation has been developed. In the stabilized formulation, acetic acid or carbonic acid is added to Reactant Mixture III. The pH of this formulation is typically about 6.2±0.2.

Upon application, the acetic acid volatilizes or, if carbonic acid is used, it converts to carbon dioxide and water. This raises the pH thereby allowing the THBP to be slowly deprotonated by the triethanolamine and complexed with the metal-amine. It is believed that the acetic acid or carbonic acid initially stabilizes the THBP and prevents the deprotonation reaction from occurring.

This stabilized photo-product coating initially becomes visible in about 24 hours upon exposure to sunlight in the presence of oxygen and continues reacting for one to two weeks thereafter, producing a fully-developed film within that time period.

The typical concentration ranges of the three reactants employed in Reactant Mixture III, in accordance with this invention, are as follows: about 0.01 to 10% of THBP, about 0.001 to 5% of at least one metal salt, preferably copper acetate, and about 0.01 to 2% of at least one amine, peferably triethanolamine. The amount of acetic acid or carbonic acid required to prevent deprotonization of THBP is usually the amount required to lower the pH of the reactant mixture to about 6 or below. Examples of these formulations are given in Table 2 hereafter.

FIG. 2 shows the infrared absorption spectrum of one particular Reactant Mixture III photo-product coating after exposure to a mercury arc vapor lamp in the presence of air for approximately 9 hours. The reactant mixture contains 4.00% THBP, 76.75% ethanol, 4.00% deionized water, 8.00% alcohol, 1.00% triethanolamine, 0.5% acetic acid (99.9% concentration), 0.75% copper acetate, and 5.00% of a polymer consisting of 60% ethyl acrylate and 40% methylmethacrylate. The infrared absorption spectrum of FIG. 2 was determined by placing a silver chloride plate in the above mixture, and leaving the plate and reactant mixture exposed to the mercury arc vapor lamp for approximately 9 hours in a normal atmosphere. After exposure, the plate was removed, washed with ethanol, then washed with acetone, dried and placed into the FTIR.

The most preferred substrate embodiment of this invention consists of a metallic substrate having on its surface an adherent photo-product coating, which coating is formed by exposing to light in the presence of an oxygen source, a reactant mixture comprising (a) 2,2',4,4'-tetrahydroxybenzophenone; (b) ammonium hydroxide; (c) at least one metal salt; and (d) at least one amine; in a solvent. Additionally, the Reactant Mixture IV method of forming an adherent photo-product coating on the surface of a metallic substrate is within the scope of this invention.

The only benzophenone found that meets the objectives of this invention and provides a suitable photo-product coating is 2,2',4,4'-tetrahydroxybenzophenone. Additionally, sources of ammonium and hydroxyl ion, other than ammonium hydroxide, have not proven effective in producing a photo-product coating of this invention in Reactant Mixture IV.

The formulas of the reaction products of this invention are unknown. It is postulated that, in the first step of the process, the ammonium hydroxide deprotonates the hydroxyl group adjacent to the THBP carbonyl group. Under the influence of light and oxygen, the deprotonated THBP is thought to form a diradical and then form both a coordination complex with the metal cation and an addition product with another THBP molecule.

Typical concentrations of the reactants of Reactant Mixture IV are given in Table 1 below:

                  TABLE 1                                                          ______________________________________                                         Reactant Mixture IV Formulations                                                        Concentration                                                                                           Most                                         Ingredients                                                                               General     Preferred  Preferred                                    ______________________________________                                         THBP       0.01 to 10% 3.0 to 5.0%                                                                               4.0%                                         NH.sub.4 OH                                                                    (28.5% conc.)                                                                             0.1 to 10%  0.25 to 1.75%                                                                             1.0%                                         (100% conc.)                                                                              0.1 to 1%   0.1 to 0.5%                                                                               0.3%                                         Metal salt 0.001 to 5% 0.05 to 0.5%                                                                              0.2%                                         Amine      0.001 to 2% 0.25 to 1% 0.6%                                         H.sub.2 O  0 to 15%    6 to 10%   8.0%                                         Alcohol    balance     balance    balance                                                 to 100%     to 100%    to 100%                                      ______________________________________                                    

These concentrations, as well as those given above for the other reactant mixtures, are provided to illustrate the present invention, but are not to be construed as limiting the invention in terms of concentration or proportion of ingredients. Concentrations outside of these general ranges can be utilized to practice this invention.

The Method of Reactant Mixture IV is typically carried out as described above for the Methods of Reactant Mixture I and II. When the reactant mixture is contacted with a metallic substrate and exposed to sunlight in the presence of oxygen, a visible photo-product coating is produced in a few hours, especially with the faster reacting metals, such as copper, manganese and iron. Exposure of this formulation to a mercury arc lamp in the presence of oxygen produces a visible photo-film within a few minutes.

Although applicants do not wish to be bound by any particular theory, the photo-ligand-metal-coordination complex of Reactant Mixture IV is believed to proceed as follows: THBP, preferably at least about 6 moles and more preferably at least about 18 moles, is mixed with at least 5 moles of ammonium hydroxide, in a suitable solvent, preferably an aqueous alcohol solvent, to form deprotonated THBP. The metal salt, preferably about 1 mole of a nickel salt is then mixed with 5 moles of an amine, preferably triethanolamine, to form a nickel salt-triethanolamine coordination complex. This complex is then mixed with the deprotonated THBP to form a metal-coordination complex that upon exposure to light in the presence of oxygen forms a photo-product of the present invention.

The photo-product coatings of this invention are insoluble in the reaction media and many other solvents, and therefore, are long lasting and durable. Once applied, the photo-product coatings cannot be removed without chemical treatment. To date, only strong solvents, such as dimethyl sulfoxide, appear to solubilize or form a complex with the photo-product coating to effect its removal. Additionally, dimethyl formamide will dissolve the coatings of Reactant Mixture I. It is known, however, that the photo-product coating will form water soluble salts with appropriate bases. For example, the photo-film can be dissolved by any strong basic material, such as sodium, potassium or ammonium hydroxide, or mixtures thereof, at pH above 10. Typically, the film is solubilized at a pH from 10.2 to 10.5. The photo-product can be precipitated as a solid from these basic solutions by the addition of an acid, such as acetic acid, to lower the pH to below about 7.0. The pH ranges of Reactant Mixtures I, II and IV typically range from about 8.5 to 9.9.

The method of cleaning the metallic substrates of this invention involves the steps of forming an adherent photo-product coating on the surface of the substrate as described above for Methods of Reactant Mixture I-IV and then removing that photo-product coating from the surface of the substrate by a solvent or basic material as described herein.

Iodine may be used in the reactant mixtures of this invention. The iodine is mixed with the reactants prior to exposure to light. The concentration of iodine that may be utilized varies from about 0.001% to about 5%, with a range of 0.01% to 1% being preferred. These percentages are weight percents based on the total weight of the composition.

The reactant mixtures of this invention also preferably employ various polymers, such as ethyl acrylate and/or methylmethacrylate, or other alcohol-soluble resin polymers, that act as a matrix so that the reactants can be easily applied to substrates such as sheet metal, and thereby allow the formation of the photo-product on the substrate.

FIG. 3 shows the infrared absorption spectrum of one particular Reactant Mixture IV photo-product coating wherein the reactant mixture contained 4.14% THBP, 86.0% ethanol, 0.63% triethanolamine, 8.00% deionized water, 1.03% ammonium hydroxide (at 28.5% conc.) and 0.2% nickel chloride, and was exposed to fluorescent light in the presence of oxygen for four days. The absorption spectrum was determined in the same manner as described for FIGS. 1 and 2.

In another aspect of this invention, the adherent photo-product coating functions as a prime coating thereby allowing the deposition or attachment of other materials to the substrates of this invention.

Other aspects and embodiments of this invention are shown in the following Examples which are illustrative of scope.

EXAMPLES 1-15

Examples 1-15 of Table 2 show typical reactant mixtures that can provide photo-product coatings in accordance with the teachings of this invention.

                                      TABLE 2                                      __________________________________________________________________________     Reactant Mixture III Formulations                                              EXAMPLES                                                                              1  2  3  4  5  6  7  8  9   10 11 12  13  14  15                        __________________________________________________________________________     Ethanol                                                                               86.7                                                                              87.3                                                                              77.2                                                                              86.3                                                                              86.1                                                                              86.39                                                                             85.6                                                                              85.0                                                                              84.96                                                                              84.5                                                                              80.5                                                                              80.5                                                                               78.5                                                                               81.75                                                                              76.9                      Deionized                                                                             8.0                                                                               8.0                                                                               8.0                                                                               8.0                                                                               8.0                                                                               8.2                                                                               8.1                                                                               8.0                                                                               7.99                                                                               8.0                                                                               8.0                                                                               --  --  --  4.0                       Water                                                                          THBP   4.0                                                                               4.0                                                                               4.0                                                                               4.0                                                                               4.0                                                                               3.94                                                                              4.0                                                                               4.5                                                                               4.59                                                                               4.5                                                                               4.0                                                                               2.0 3.5 4.0 4.0                       TEA    0.5                                                                               0.6                                                                               0.6                                                                               1.0                                                                               1.0                                                                               1.1                                                                               1.07                                                                              1.0                                                                               1.1 1.0                                                                               1.0                                                                               1.0 1.0 1.0 1.0                       Metal  0.4.sup.(1)                                                                       0.21.sup.(2)                                                                      0.2.sup.(2)                                                                       0.2.sup.(3)                                                                       0.2.sup.(3)                                                                       0.5.sup.(3)                                                                       1.0.sup.(3)                                                                       1.0.sup.(3)                                                                       0.99.sup.(4)                                                                       1.0.sup.(3)                                                                       1.0.sup.(3)                                                                       1.0.sup.(3)                                                                        1.5.sup.(3)                                                                        0.75.sup.(3)                                                                       1.0.sup.(3)               Salt                                                                           Acetic 0.4                                                                               0.1                                                                               10.0                                                                              0.5                                                                               0.5                                                                               0.54                                                                              0.54                                                                              0.5                                                                               0.65                                                                               0.5                                                                               0.5                                                                               0.5 0.5 0.5 1.0.sup.(g)               Acid.sup.(a)                                                                   Stearyl.sup.(d)                                                                       -- -- -- -- 0.2.sup.(d)                                                                       -- -- -- --  -- 8.0.sup.(e)                                                                       10.0.sup.(e)                                                                       10.0.sup.(e)                                                                       8.0.sup.(e)                                                                        8.0                       or benzyl.sup.(e)                                                              alcohol                                                                        Matrix -- -- -- -- -- -- -- -- --  0.5.sup.(b)                                                                       5.0.sup.(c)                                                                       5.0.sup.(c)                                                                        5.0.sup.(c)                                                                        4.0.sup.(c)                                                                        5.0.sup.(c)               Polymer                                                                        __________________________________________________________________________      .sup.(1) silver acetate                                                        .sup.(2) FeCl.sub.2.4H.sub.2 O                                                 .sup.(3) copper acetate                                                        .sup.(4) zinc acetate                                                          .sup.(a) 99.9% concentrated acetic acid                                        .sup.(b) Carbsoset 525 B. F. Goodrich                                          .sup.(c) 60% ethyl acrylate and 40% methylmethacrylate                         .sup.(g) Co.sub.2 gas                                                    

EXAMPLES 16-25

The Reactant Mixture IV formulas of Table 3 also show typical reactant mixtures in accordance with the teachings of this invention.

                                      TABLE 3                                      __________________________________________________________________________     Reactant Mixture IV Formulations                                               EXAMPLES                                                                              16 17 18 19 20  21 22 23 24 25                                          __________________________________________________________________________     Ethanol                                                                               86.0                                                                              87.4                                                                              90.85                                                                             86.0                                                                              86.0.sup.(a)                                                                       86.1                                                                              95.4                                                                              86.1                                                                              86.2                                                                              86.2                                        THBP   4.0                                                                               2.0                                                                               3.0                                                                               4.14                                                                              4.14                                                                               4.0                                                                               2.0                                                                               4.0                                                                               4.0                                                                               4.0                                         TEA    0.5                                                                               0.5                                                                               0.75                                                                              0.63                                                                              0.63                                                                               0.5                                                                               0.5                                                                               0.5                                                                               0.6                                                                               0.6                                         NH.sub.4 OH                                                                           1.0                                                                               1.0                                                                               5.0                                                                               1.03                                                                              1.03                                                                               1.0                                                                               1.0                                                                               1.0                                                                               1.0                                                                               1.0                                         (28.5%)                                                                        Deionized                                                                             8.0                                                                               8.0                                                                               -- 8.0                                                                               8.0 8.0                                                                               -- 8.0                                                                               8.0                                                                               8.0                                         Water                                                                          Metal  0.5.sup.(1)                                                                       0.1.sup.(1)                                                                       0.4.sup.(1)                                                                       0.2.sup.(1)                                                                       0.2.sup.(1)                                                                        0.4.sup.(2)                                                                       0.1.sup.(3)                                                                       0.4.sup.(4)                                                                       0.2.sup.(5)                                                                       0.2.sup.(6)(7)                              Salt                                                                           Benzyl 1.0                                                                               -- -- -- --  -- 1.0                                                                               -- -- --                                          Alcohol                                                                        __________________________________________________________________________      .sup.(1) NiCl.sub.2.H.sub.2 O                                                  .sup.(2) silver acetate                                                        .sup.(3) iron chloride (FeCl.sub.2.H.sub.2 O)                                  .sup.(4) copper acetate monohydrate                                            .sup.(5) MnCl.sub.2.4H.sub.2 O                                                 .sup.(6) ZnCl.sub.2                                                            .sup.(7) CuCl.sub.2.H.sub.2 O                                                  .sup. (a) isopropanol                                                    

EXAMPLES 26-27

In Examples 26 and 27, two steel Q-Panels (Type QD-35, smooth finish, 0.020 inch thickness, ASTM Specification D609.3B and Type R, matte finish, 0.032 inch thickness, ASTM Specification D6091.B, both from The Q-Panel Company, 26200 First Street, Cleveland, Ohio 44145) were placed in a reactant mixture bath and exposed to a mercury arc lamp (Gates MLA 85 watt medium pressure) for 3 hours. The steel Q-Panels were then left in the reactant mixture (4.0% THBP, 84.3% ethanol, 0.6% triethanolamine, 10.0% deionized water, 1.0% ammonium hydroxide (28.5% conc.), and 0.1% PbCl₂) for an additional 9 hours after their exposure to light. After removal from the reactant mixture, the Q-Panels were washed with ethanol, then acetone, blow dried and observed. Both panels were pink to brown in color.

EXAMPLES 28-29

Examples 28 and 29 were prepared by exposing a QD-35 steel Q-Panel and a galvanized sheet metal panel to a nickel Formula IV reactant mixture in the presence of the mercury arc lamp referred to in the Example above. The oxygen source in these examples as in all others was air. The reactant mixture consisted of 4.14% THBP, 86.0% ethanol, 0.63% triethanolamine, 8.0% deionized water, 1.03% ammonium hydroxide (28.5% conc.), and 0.2% nickel chloride. Both panels were exposed to the mercury arc lamp and the reactant mixture for 3 hours and then left in the reactant mixture for an additional 9 hours after exposure to light. The panels were then removed from the reactant mixture, washed in alcohol, washed again in acetone, and blow dried. The galvanized sheet metal displayed a dark to light blue color film, while the QD-35 Q-Panel had a blue to bronze coating.

EXAMPLES 30-31

In Examples 30 and 31 aluminum Q-Panels, A 35 and AL-35, were exposed to the same reactant mixture and under the same conditions as used in Examples 28 and 29. Both panels had a dark blue coating when viewed from one angle and appeared greenish bronze in color when viewed from a different angle. The Type A Q-Panel is a bare 3003 H14 aluminum panel, 0.25 inches thick. The Type AL Q-Panel is made of the same aluminum as Type A except that it is treated with Alodine 12005. Alodine is a chromium oxide conversion coating.

EXAMPLES 32-44

In Examples 32 through 44, the metallic substrates shown in Table 4 were photo-coated with a reactant mixture consisting of 4.14% THBP, 86.0% ethanol, 0.63% triethanolamine, 8.0% deionized water, 1.03% ammonium hydroxide (28.5% conc.), and 0.2% nickel chloride. The metallic substrates were coated with this reactant mixture (which was previously exposed to laboratory room light for approximately 7 days) by contacting the reactant mixture and metallic substrate and exposing both to sunlight through a laboratory window for approximately 10 hours. The color of each photo-product coating is shown in Table 4.

                  TABLE 4                                                          ______________________________________                                         Example No. Metallic Substrate                                                                             Coating Color                                      ______________________________________                                         32          Inco 718 Steel  Bright blue                                        33          Waspallox Steel Light blue                                         34          Titanium        Light blue                                         35          Tungston        Dark blue                                          36          Copper wire     Bluish black                                       37          Iron Q-Panel    Orange to blue                                     38          Platinum wire   Light blue                                         39          Inco Nickel powder                                                                             Dark color                                                     (type 255)                                                         40          Gold (14 karat) Blue yellow                                        41          Polished aluminum                                                                              Blue                                               42          Nickel          --                                                 43          Silver          Blue                                               44          Zinc wire       Blue                                               ______________________________________                                    

EXAMPLE 45

Corrosion is a general term applied to the process in which uncombined metals change over to compounds. In the special case of iron, the corrosion process is called rusting. The most direct approach to prevent rusting is to shut off the reactants, O₂ and H₂ O. As demonstrated by this example, corrosion can be inhibited by coating metallic substrates with the photo-product coatings of this invention.

In this Example, coated metallic substrates were prepared from strips of QD-35 steel Q-Panels. These Q-Panels were separately exposed to the four reactant mixtures shown in Table 5 in the presence of the fluorescent lights in the laboratory for approximately 24 hours.

                  TABLE 5                                                          ______________________________________                                         Reactant Mixture                                                                             Concentration (in weight percent)                                Composition   A       B        C     D                                         ______________________________________                                         THBP          4.0     4.0      4.0   4.0                                       Ethanol       86.0    85.9     85.2  85.9                                      TEA.sup.1     0.6     0.6      0.6   0.6                                       Deionized H.sub.2 O                                                                          8.0     8.0      8.0   8.0                                       NH.sub.4 OH (28.5% conc.)                                                                    1.0     1.0      1.0   1.0                                       Metal Salt    0.2.sup.3                                                                              --       0.2.sup.4                                                                            0.2.sup.4                                 Iodine        --      0.5      1.0   0.3                                       TBA--Br.sup.2 0.2     --       --    --                                        ______________________________________                                          .sup.1 TEA = triethanolamine                                                   .sup.2 TBA--Br is tetra butylammonium bromide.                                 .sup.3 nickel chloride                                                         .sup.4 copper acetate                                                    

After exposure, the Q-Panels were removed from the reactant mixture, washed with alcohol and air dried for 24 hours. The lower portion of each of the 4 coated metallic substrates were then placed in tap water for 48 hours. All coatings resisted rusting during this test except for the cut edges of the Q-Panels coated with reactant mixtures A and B.

The coated Q-Panels were then placed in tap water for an additional 48 hours and again examined. Fo the Q-Panel coated with reactant mixture A, the panel side not exposed to the light rusted. The panel side exposed to light also rusted but it had a film layer underneath the rust. The Q-Panel coated with reactant mixture B also had some rust on the side not exposed to light, but the side exposed to light appeared normal without rust. When this Q-Panel was viewed under a microscope, no rust was visible. As for the Q-Panels coated with reactant mixtures C and D, the sides exposed to the light appeared normal without the presence of rust.

EXAMPLE 46

As shown in this Example, the photo-product coatings of this invention, have the ability to change the electronegativity of metals and therefore show potential as a coating for battery electrodes.

To demonstrate this property, a battery cell was assembled using two copper wires (each 1 mm thick) submerged in a beaker of tap water to a depth of 40 mm and at a distance of 40 mm between the two copper wire electrodes. Throughout the testing, one copper wire remained uncoated, while the other was either an uncoated control or a coated test electrode. A regulated power supply was attached to this circuit and set at 0.5 volts of DC current. The current measured with the control copper wire was 32 micro amps. The experiment was then repeated with a copper wire that had been photo coated with a reactant mixture (Example 46A) consisting of 4.0% THBP, 86.2% ethanol, 0.6% triethanolamine, 8.0% deionized water, 1.0% ammonium hydroxide (28.5% conc.), and 0.2% lead chloride, upon exposure to sunlight through a laboratory window for approximately 10 hours. This coated wire exhibited a current of 26 micro amps. When another copper wire was coated with a reactant mixture (Example 46B) consisting of 4.0% THBP, 85.2% ethanol, 0.6% triethanolamine, 8.0% deionized water, 1.0% ammonium hydroxide (28.5% conc.), 0.2% copper acetate, and 1.0% iodine by exposure to sunlight through a laboratory window for approximately 10 hours, it exhibited a current of 86 micro amps in the battery cell.

When a volt meter was hooked up to the above referenced battery cell, the following voltages were recorded. Control (uncoated copper): 1.5 millivolts; Reactant Mixture Example 46A: 40 millivolts; and Reactant Mixture Example 46B: 50 millivolts.

EXAMPLE 47

In this Example, the reactant mixture consisted of 4.0% THBP, 86.0% ethanol, 0.3% iodine, 0.6% triethanolamine, 8.0% deionized water, 1.0% ammonium hydroxide (28.5% conc.), and 0.1% iron chloride. Three Q-Panels, QD-35, R-35 and AC 35, were placed in a bath of this reactant mixture and exposed for 3 hours to the mercury arc lamp described in the Examples above. After exposure to light, the Q-Panels were left in the bath for an additional 21 hours. After cleaning with ethanol, then acetone and drying, the QD-35 steel Q-Panel was brown metallic pink in color, the R Q-Panel was similar in color with a slight blue hue, and the aluminum AL-35 Q-Panel was light brown.

EXAMPLES 48-54

Additional examples of reactant mixtures within the teachings of the invention are:

EXAMPLE 48:

4.0% 2,2',4,4'-tetrahydroxybenzophenone, 86.2% ethanol, 0.6% triethanolamine, 8.0% deionized water, 1.0% ammonium hydroxide (28.5% conc.), and 0.2% HgCl₂.

EXAMPLE 49:

4.0% 2,2',4,4'-tetrahydroxybenzophenone, 86.2% ethanol, 0.6% triethanolamine, 8.0% deionized water, 1.0% ammonium hydroxide (28.5% conc.), and 0.2% PdCl₂.

EXAMPLE 50:

4.0% 2,2',4,4'-tetrahydroxybenzophenone, 86.2% ethanol, 0.6% triethanolamine, 8.0% deionized water, 1.0% ammonium hydroxide (28.5% conc.), and 0.2% CdCl₂.

EXAMPLE 51:

4.0% 2,2',4,4'-tetrahydroxybenzophenone, 86.2% ethanol, 0.6% triethanolamine, 8.0% deionized water, 1.0% ammonium hydroxide (28.5% conc.), and 0.2% RuCl₃.

EXAMPLE 52:

4.0% 2,2',4,4'-tetrahydroxybenzophenone, 86.2% ethanol, 0.6% triethanolamine, 8.0% deionized water, 1.0% ammonium hydroxide (28.5% conc.) and 0.2% ZrO₂.

EXAMPLE 53:

4.0% 2,2',4,4'-tetrahydroxybenzophenone, 86.2% ethanol, 0.6% triethanolamine, 8.0% deionized water, 1.0% ammonium hydroxide (28.5% conc.), and 0.2% RhCl₃.

EXAMPLE 54:

3.0% 2,2',4,4'-tetrahydroxybenzophenone, 2.0% triethanolamine, 0.1% cobalt chloride (CoCl₂), and 94.9% ethanol. 

What is claimed is:
 1. A metallic substrate having on its surface an adherent photo-product coating, which coating is formed by exposing to light in the presence of an oxygen source, a reactant mixture having a pH from about 7 to 10.5 comprising:(a) 2,2',4,4'-tetrahydroxybenzophenone; (b) ammonium hydroxide; and (c) optionally a trace amount of at least one reactive metal selected from the group consisting of zinc, copper, nickel, silver, iron, manganese, lead, cobalt, zirconium, mercury, palladium, cadmium, ruthenium, rhodium, and mixtures thereof;in a solvent.
 2. A metallic substrate having on its surface an adherent photo-product coating, which coating is formed by exposing to light in the presence of an oxygen source, a reactant mixture having a pH from about 7 to 10.5 comprising:(a) 2,2',4,4'-tetrahydroxybenzophenone; (b) ammonium hydroxide; and (c) at least one metal salt wherein the metal is selected from the group consisting of zinc, copper, nickel, silver, iron, manganese, lead, cobalt, zirconium, mercury, palladium, cadmium, ruthenium, rhodium, and mixtures thereof;in a solvent.
 3. A metallic substrate having on its surface an adherent photo-product coating, which coating is formed by exposing to light in the presence of an oxygen source, a reactant mixture having a pH from about 7 to 10.5 comprising:(a) 2,2',4,4'-tetrahydroxybenzophenone; (b) at least one metal salt wherein the metal is selected from the group consisting of zinc, copper, nickel, silver, iron, manganese, lead, cobalt, zirconium, mercury, palladium, cadmium, ruthenium, rhodium, and mixtures thereof; and (c) at least one amine;in a solvent.
 4. A metallic substrate having on its surface an adherent photo-product coating, which coating is formed by exposing to light in the presence of an oxygen source, a reactant mixture having a pH from about 7 to 10.5 comprising:(a) 2,2',4,4'-tetrahydroxybenzophenone; (b) ammonium hydroxide; (c) at least one metal salt wherein the metal is selected from the group consisting of zinc, copper, nickel, silver, iron, manganese, lead, cobalt, zirconium, mercury, palladium, cadmium, ruthenium, rhodium, and mixtures thereof; and (d) at least one amine;in a solvent.
 5. The substrate of claims 2, 3 or 4 wherein the metal salt is selected from the group consisting of nickel chloride, cobalt chloride, silver acetate, iron chloride, copper acetate, lead chloride, zinc acetate, copper chloride and mixtures thereof.
 6. The substrate of claims 3 or 4 wherein the amine is selected from the group consisting of triethanolamine, diethanolamine, ethanolamine, monomethanolamine, butylamine, n-amylamine and mixtures thereof.
 7. The substrate of claims 1, 2, 3 or 4 in which the metallic substrate is selected from the group consisting of steel, titanium, tungsten, copper, iron, platinum, nickel, gold, aluminum, silver, zinc and alloys and composites thereof.
 8. A metallic substrate having on its surface an adherent photo-product coating containing the elements carbon, hydrogen, oxygen, nitrogen and a trace amount of zinc; exhibiting characteristic absorption peaks in the infrared region of the spectrum, when cast as a film on a silver chloride plate at the following frequencies expressed in reciprocal centimeters: 1616, 1543, 1517, 1463, 1400, 1367, 1233, 1191, 1106, 996, 977, 845 and 805; and formed by exposing to light in the presence of an oxygen source, a reactant mixture comprising: 2,2',4,4'-tetrahydroxybenzophenone, ammonium hydroxide and a trace amount of zinc.
 9. A metallic substrate having on its surface an adherent photo-product coating containing the elements carbon, hydrogen, nitrogen, oxygen and copper; exhibiting characteristic absorption peaks in the infrared region of the spectrum, when cast as a film on a silver chloride plate at the following frequencies expressed in reciprocal centimeters: 1734, 1617, 1377, 1234, 1161, 1125, and 1114; and formed by exposing to light in the presence of an oxygen source, a reactant mixture comprising: 2,2',4,4'-tetrahydroxybenzophenone, triethanolamine and copper cation.
 10. A metallic substrate having on its surface an adherent photo-product coating containing the elements carbon, hydrogen, nitrogen, oxygen and nickel; exhibiting characteristic absorption peaks in the infrared region of the spectrum, when cast as a film on a silver chloride plate, at the following frequencies expressed in reciprocal centimeters: 1747, 1606, 1581, 1440, 1266, 1226, 1153, 1120, 1097, 972, 875 and 751; and formed by exposing to light in the presence of an oxygen source a reactant mixture comprising: 2,2',4,4'-tetrahydroxybenzophenone, triethanolamine, ammonium hydroxide and nickel cation.
 11. A method of forming an adherent photo-product coating on the surface of a metallic substrate comprising the steps of:(1) preparing the reactant mixture of claim 1; (2) contacting said substrate with said reactant mixture; and (3) exposing said reactant mixture in contact with said substrate to light in the presence of an oxygen source.
 12. A method of forming an adherent photo-product coating on the surface of a metallic substrate comprising the steps of:(1) preparing a reactant mixture of claim 2; (2) contacting said substrate with said reactant mixture; and (3) exposing said reactant mixture in contact with said substrate to light in the presence of an oxygen source.
 13. A method of forming an adherent photo-product coating on the surface of a metallic substrate comprising the steps of:(1) preparing a reactant mixture of claim 3; (2) contacting said substrate with said reactant mixture; and (3) exposing said reactant mixture in contact with said substrate to light in the presence of an oxygen source.
 14. A method of forming an adherent photo-product coating on the surface of a metallic substrate comprising the steps of:(1) preparing a reactant mixture of claim 4; (2) contacting said substrate with said reactant mixture; and (3) exposing said reactant mixture in contact with said substrate to light in the presence of an oxygen source.
 15. The method of claims 13 or 14 wherein the metal salt is selected from the group consisting of nickel chloride, cobalt chloride, silver acetate, iron chloride, copper acetate, lead chloride, zinc acetate, copper chloride and mixtures thereof.
 16. The method of claims 13 or 14 wherein the amine is selected from the group consisting of triethanolamine, diethanolamine, ethanolamine, monomethanolamine, butylamine, n-amylamine and mixtures thereof.
 17. The method of claims 11, 12, 13 or 14 wherein said metallic substrate is selected from the group consisting of steel, titanium, tungsten, copper, iron, platinum, nickel, gold, aluminum, silver, zinc and alloys and composites thereof.
 18. A method of cleaning a metallic substrate comprising the steps of:(A) forming an adherent photo-product coating on the surface of said substrate by:(1) preparing a reactant mixture of claim 1; (2) contacting said substrate with said reactant mixture; and (3) exposing said reactant mixture in contact with said substrate to light in the presence of an oxygen source; and (B) removing said photo-product coating from the surface of said substrate.
 19. A method of cleaning a metallic substrate comprising the steps of:(A) forming an adherent photo-product coating on the surface of said substrate by:(1) preparing a reactant mixture of claim 2; (2) contacting said substrate with said reactant mixture; and (3) exposing said reactant mixture in contact with said substrate to light in the presence of an oxygen source; and (B) removing said photo-product coating from the surface of said substrate.
 20. A method of cleaning a metallic substrate comprising the steps of:(A) forming an adherent photo-product coating on the surface of said substrate by:(1) preparing a reactant mixture of claim 3; (2) contacting said substrate with said reactant mixture; and (3) exposing said reactant mixture in contact with said substrate to light in the presence of an oxygen source; and (B) removing said photo-product coating from the surface of said substrate.
 21. A method of cleaning a metallic substrate comprising the steps of:(A) forming an adherent photo-product coating on the surface of said substrate by:(1) preparing a reactant mixture of claim 4; (2) contacting said substrate with said reactant mixture; and (3) exposing said reactant mixture in contact with said substrate to light in the presence of an oxygen source; and (B) removing said photo-product coating from the surface of said substrate.
 22. The method of cleaning of claims 18, 19, 20 or 21 wherein the photo-product coating is removed by contact with a basic material.
 23. The method of cleaning of claims 18, 19, 20 or 21 wherein the photo-product coating is removed by contact with a solvent. 